Dye mixtures containing azo dyes having a coupling component from the diaminopyridine series

ABSTRACT

Dye mixtures comprising at least six isochromatic dyes of the formula ##STR1## where D is the radical of a diazo component of the aniline, aminothiophene, aminothiazole, aminoisothiazole or aminobenzisothiazole series and 
     one of the radicals X 1  and X 2  is amino and the other is a radical of the formula ##STR2## where L is unsubstituted or substituted C 2  -C 8  -alkylene 
     R 1  is hydrogen or unsubstituted or substituted C 1  -C 4  -alkyl and 
     R 2  is hydrogen, C 1  -C 4  -alkyl, benzyl, phenyl, or C 1  -C 8  -alkanoyl, 
     and the use thereof for dyeing or printing textile materials, and dye mixtures comprising thienylazopyridine dyes and anthraquinone dyes and the use thereof for dyeing or printing textile materials.

This is a division, of application Ser. No. 08/159,301 filed on Nov. 30,1993 now U.S. Pat. No. 5,403,363.

The present invention relates to novel dye mixtures comprising at leastsix isochromatic dyes of the formula I ##STR3## where D is the radicalof a diazo component from the aniline, aminothiophene, aminothiazole,aminoisothiazole or aminobenzisothiazole series and

one of the radicals X¹ and X² is amino and the other is a radical of theformula ##STR4## where L is C₂ -C₈ -alkylene which is uninterrupted orinterrupted by one or two oxygen atoms in an ether function,

R¹ is hydrogen or C₁ -C₄ -alkyl which is unsubstituted or substituted byhydroxyl, C₁ -C₄ -alkoxy or C₁ -C₈ -alkanoyloxy, and

R² is hydrogen, C₁ -C₄ -alkyl, benzyl, phenyl or C₁ -C₈ -alkanoyl

and the use thereof for dyeing or printing textile materials, and to dyemixtures comprising thienylazopyridine dyes and anthraquinone dyes andthe use thereof for dyeing or printing textile materials.

The individual dyes of the abovementioned dye mixtures or alternativelymixtures which contain up to four individual components are alreadyknown from U.S. Pat. No. 4,855,412, U.S. Pat. No. 4,855,413 orEP-A-201,896.

However, it has been shown that the dyes of the prior art still havedeficiencies in their application properties. A strong temperaturedependence of the absorption behavior of the dyes, the tendency of thedispersed dyes or dye mixtures to recrystallize and an inadequate bathexhaustion can be mentioned here in particular.

It is an object of the present invention to provide novel dye mixtureswhich are free of the abovementioned deficiencies.

We have found that this object can be achieved by the dye mixturesfurther described at the beginning.

All alkyl and alkylene groups occurring in the dye components of the dyemixtures according to the invention can be either straight-chain orbranched.

If substituted alkyl groups occur in the dye components, as a rule thesehave 1 or 2 substituents.

If substituted phenyl groups occur in the dye components, as a rulethese have 1 to 3, preferably 1 or 2, substituents.

Preferred dye mixtures according to the invention are those where

D is a radical of the formula ##STR5## where Z¹ is hydrogen, nitro,cyano, C₁ -C₉ -alkoxycarbonyl which can be interrupted by one or twooxygen atoms in an ether function, C₁ -C₉ -alkylaminocarbonyl which canbe interrupted by one or two oxygen atoms in an ether function,trifluoromethyl, C₁ -C₄ -alkylsulfonyl, 3-(C₁ -C₄-alkyl)-1,2,4-oxadiazol-5-yl or 3-phenyl-1,2,4-oxadiazol-5-yl,

Z² is hydrogen, chlorine, bromine, cyano, methyl, methoxy, ethoxy,phenylazo or benzoyl which is unsubstituted or substituted by methyl,methoxy or chlorine,

Z³ is hydrogen, cyano, chlorine, bromine or C₁ -C₉ -alkoxycarbonyl whichcan be interrupted by one or two oxygen atoms in an ether function, orZ² and Z³ together are a radical of the formula CO-NA¹ -CO, where A¹ hasthe meaning of hydrogen or C₁ -C₄ -alkyl,

Z⁴ is cyano, formyl, nitro, C₁ -C₉ -alkoxycarbonyl which can beinterrupted by one or two oxygen atoms in an ether function, or isunsubstituted or cyano-substituted phenylazo or a radical of the formula##STR6## where A² has the meaning of cyano or C₁ -C₉ -alkoxycarbonylwhich can be interrupted by one or two oxygen atoms in an etherfunction,

Z⁵ is hydrogen, C₁ -C₄ -alkyl, C₁ -C₄ -alkoxy, phenyl which isunsubstituted or substituted by methyl, methoxy or chlorine, benzylwhich is unsubstituted or substituted by methyl, methoxy or chlorine, C₁-C₄ -alkylsulfonyl, chlorine, bromine or C₁ -C₉ -alkoxycarbonyl whichcan be interrupted by one or two oxygen atoms in an ether function,

Z⁶ is C₁ -C₄ -alkyl, phenyl which is unsubstituted or substituted bymethyl, methoxy or chlorine, benzyl which is unsubstituted orsubstituted by methyl, methoxy or chlorine, cyano, nitro, C₁ -C₉-alkoxycarbonyl which can be interrupted by one or two oxygen atoms inan ether function, or C₁ -C₄ -alkylsulfonyl,

Z⁷ is C₁ -C₄ -alkyl, phenyl which is unsubstituted or substituted bymethyl, methoxy or chlorine, benzyl which is unsubstituted orsubstituted by methyl, methoxy or chlorine, or C₁ -C₄ -alkylsulfonyl,and

Z⁸ is nitro, cyano or C₁ -C₄ -alkylsulfonyl.

If D is a radical of the formula IIa, those dyes are preferred in whichat least one of the radicals Z¹, Z² and Z³ is other than hydrogen.

R¹, R², Z⁵, Z⁶, Z⁷ and A¹ radicals are eg. methyl, ethyl, propyl,isopropyl, butyl, isobutyl or sec-butyl.

Z⁵, Z⁶ and Z⁸ radicals are, like Z¹ radicals, furthermore eg.methylsulfonyl, ethylsulfonyl, propylsulfonyl, isopropylsulfonyl,butylsulfonyl, isobutylsulfonyl or sec-butylsulfonyl.

Z¹, Z⁵ and Z⁶ radicals are, like Z³, Z⁴ and A² radicals, furthermore eg.methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, isopropoxycarbonyl,butoxycarbonyl, isobutoxycarbonyl, sec-butoxycarbonyl,pentyloxycarbonyl, isopentyloxycarbonyl, neopentyloxycarbonyl,tert-pentyloxycarbonyl, hexyloxycarbonyl, 2-methylpentyloxycarbonyl,heptyloxycarbonyl, 2-methylhexyloxycarbonyl, octyloxycarbonyl,isooctyloxycarbonyl, 2-ethylhexyloxycarbonyl, nonyloxycarbonyl orisononyloxycarbonyl.

Z¹ radicals are furthermore eg. methylaminocarbonyl, ethylaminocarbonyl,propylaminocarbonyl, isopropylaminocarbonyl, butylaminocarbonyl,isobutylaminocarbonyl, sec-butylaminocarbonyl, pentylaminocarbonyl,isopentylaminocarbonyl, neopentylaminocarbonyl,tert-pentylaminocarbonyl, hexylaminocarbonyl,2-methylpentylaminocarbonyl, heptylaminocarbonyl,2-methylhexylaminocarbonyl, octylaminocarbonyl, isooctylaminocarbonyl,2-ethylhexylaminocarbonyl, nonylaminocarbonyl or isononylaminocarbonyl.

R² radicals are furthermore eg. formyl, acetyl, propionyl, butyryl,isobutyryl, pentanoyl, isopentanoyl, hexanoyl, heptanoyl, octanoyl or2-ethylhexanoyl.

R¹ radicals are furthermore eg. 2-hydroxyethyl, 2- or 3-hydroxypropyl,2- or 4-hydroxybutyl, 2-methoxyethyl, 2-ethoxyethyl, 2-propoxyethyl,2-isopropoxyethyl, -butoxyethyl, 2- or 3-methoxypropyl, 2- or3-ethoxypropyl, 2- or 3-propoxypropyl, 2- or 3-isopropoxypropyl, 2- or3-butoxypropyl, 2- or 4-methoxybutyl, 2- or 4-ethoxybutyl, 2- or4-propoxybutyl, 2- or 4-isopropoxybutyl, 2- or 4-butoxybutyl,2-formyloxyethyl, 2-acetyloxyethyl, 2-propionyloxyethyl,2-butyryloxyethyl, 2-isobutyryloxyethyl, 2-pentanoyloxyethyl,2-isopentanoyloxyethyl, 2-hexanoyloxyethyl, 2-heptanoyloxyethyl,2-octanoyloxyethyl, 2- (2-ethylhexanoyloxy)ethyl, 2- or3-formyloxypropyl, 2- or 3-acetyloxypropyl, 2- or 3-propionyloxypropyl,2- or 3-butyryloxypropyl, 2- or 3-isobutyryloxypropyl, 2- or3-pentanoyloxypropyl, 2- or 3-isopentanoyloxypropyl, 2- or3-hexanoyloxypropyl, 2- or 3-heptanoyloxypropyl, 2- or3-octanoyloxypropyl, 2- or 3-(ethylhexanoyloxy)propyl, 2- or4-formyloxybutyl, 2- or 4-acetyloxybutyl, 2- or 4-propionyloxybutyl, 2-or 4-butyryloxybutyl, 2- or 4-isobutyryloxybutyl, 2- or4-pentanoyloxybutyl, 2- or 4-hexanoyloxybutyl, 2- or4-heptanoyloxybutyl, 2- or 4-octanoyloxybutyl or 2- or4-(2-ethylhexanoyloxy)butyl.

Z⁵ radicals are furthermore eg. methoxy, ethoxy, propoxy, isopropoxy,butoxy, isobutoxy or sec-butoxy.

Z⁵, Z⁶ and Z⁷ radicals are furthermore eg. phenyl, 2-, 3- or4-methylphenyl, 2,4-dimethylphenyl, 2-, 3- or 4-methoxyphenyl,2,4-dimethoxyphenyl, 2-, 3- or 4-chlorophenyl, 2,4-dichlorophenyl,2-methyl-4-chlorophenyl, 2-methyl-4-methoxyphenyl, benzyl, 2-, 3- or4-methylbenzyl, 2-, 3- or 4-methoxybenzyl or 2-, 3- or 4-chlorobenzyl.

L radicals are eg. CH₂, (CH₂)₂, (CH₂)₃, (CH₂)₄, (CH₂)₅, (CH₂)₆, (CH₂)₇,(CH₂)₈, CH(CH₃)CH₂, CH(CH₃)CH(CH)₃, (CH₂)₂ O(CH₂)₂, (CH₂)₂ O(CH₂)₃,(CH₂)₃ O(CH₂)₃, (CH₂)₃ O(CH₂)₄, (CH₂)₄ O(CH₂)₄, CH(CH₃)CH₂ OCH₂ CH(CH₃)or (CH₂)₂ O(CH₂)₂ O(CH₂)₂. Z² radicals are eg. benzoyl, 2-, 3- or4-methylbenzoyl, 2-, 3- or 4-methoxybenzoyl or 2-, 3- or4-chlorobenzoyl.

Preferred dye mixtures according to the invention are furthermore thosecontaining 6 to 12, in particular 6 to 8 or 10 to 12, isochromatic dyesof the formula I, where dye mixtures according to the inventioncontaining 8 isochromatic dyes of the formula I are particularly to beemphasized.

Particularly preferred dye mixtures according to the invention are thosewhere D is a radical of the formula IIb, IIc or IId, where a radical ofthe formula IIb is particularly to be emphasized.

Particularly preferred dye mixtures according to the invention arefurthermore those where R² is C₁ -C₅ -alkanoyl and L is C₄ -C₈ -alkylenewhich is interrupted by 1 or 2 oxygen atoms in an ether function.

Very particularly preferred dye mixtures according to the invention arethose where L is a radical of the formula (CH₂)₂ O(CH₂)₂, (CH₂)₂O(CH₂)₃, (CH₂)₃ O(CH₂)₃, (CH₂)₃ O(CH₂)₄ or (CH₂)₂ O(CH₂)₂ O(CH₂)₂.

Very particularly preferred dye mixtures according to the invention arefurthermore those where R² is acetyl.

Very particularly preferred dye mixtures according to the invention arefurthermore those where D is a radical of the formula III ##STR7## whereY¹ is methyl or chlorine and

Y² is cyano or formyl.

The novel dye mixtures can be obtained eg. by the method described inthe following.

For example, 2,6-dichloro-3-cyano-4-methylpyridine can be converted withammonia in a manner known per se into the correspondingaminochloropyridines of the formulae IVa and IVb ##STR8## where theisomers IVa and IVb are formed in the molar ratio 3:17 to 2:3.

In a subsequent reaction, the aminochloropyridines IVa/IVb can bereacted with a mixture of at least two amines of the formula V ##STR9##where L and R¹ in each case have the abovementioned meaning and R³ ishydrogen, C₁ -C₄ -alkyl, benzyl or phenyl. The amines of the formula Vmust differ here in at least one of the variables L, R¹ and R³ andadditionally R³ must be hydrogen in at least one amine of the formula V.

In this reaction, the diaminopyridine mixtures of the formulae VIa andVIb ##STR10## result, where L and R¹ in each case have theabovementioned meaning, in the appropriate molar ratio.

Following this, the resulting diaminopyridine mixture can be

a) first acylated, which can be carried out eg. by reaction with acarboxylic acid of the formula VII

    R.sup.4 --OH                                               (VII),

where R⁴ is C₁ -C₈ -alkanoyl, in the presence or absence of mineralacid, and

b) then coupled with a diazonium salt which is derived from an amine ofthe formula VIII

    D--NH.sub.2                                                (VIII),

where D has the abovementioned meaning.

If R¹ in formula VIa/VIb is hydroxy-substituted C₁ -C₄ -alkyl, a doubleacylation is carried out in step a).

However, the coupling of the diaminopyridine mixture with the diazoniumsalt can be carried out first and the acylation reaction can be carriedout subsequently. This last-mentioned procedure is preferred.

In this method, during the precipitation of the dye mixture from thecarboxylic acid, the mixture is obtained in high purity and in optimumcrystal shape and crystal size. This minimizes the expense of dispersingthe dye mixtures which is necessary before use and prevents theircrystal growth in the dye liquor.

In many cases, the dye mixtures according to the invention are obtainedin a mixture of two different crystal modifications.

The novel dye mixtures are advantageously suited to the dyeing orprinting of textile materials. These are eg. fibers or fabric, inparticular of polyesters, in addition also of cellulose esters orpolyamides, or a blended fabric of polyesters and cellulose fibers orwool.

The dye mixtures according to the invention show virtually notemperature dependence on the absorption behavior of the dyes. Theyadditionally have a high bath exhaustion and their tendency torecrystallize in dispersed form is very low.

The present invention furthermore relates to novel dye mixturescomprising one or more red azo dyes of the formula IX ##STR11## whereone of U¹ and U² is a radical of the formula ##STR12## and the other isa radical of the formula NH-B, where L is C₂ -C₈ -alkylene, which may beinterrupted by 1 or 2 oxygen atoms in ether function,

R¹ is hydrogen or C₁ -C₄ -alkyl, which may be substituted by hydroxyl,C₁ -C₄ -alkoxy or C₁ -C₈ -alkanoyloxy,

R² is hydrogen, C₁ -C₄ -alkyl, benzyl, phenyl or C₁ -C₈ -alkanoyl and

B is hydrogen, C₁ -C₄ -alkyl which may be hydroxyl-substituted, or aradical of the formula L-O-R², where L and R² are each as defined above,

U³ is hydrogen or C₁ -C₄ -alkyl,

Q¹ is cyano, formyl, nitro or C₁ -C₉ -alkoxycarbonyl, which may beinterrupted by 1 or 2 oxygen atoms in ether function,

Q² is hydrogen, C₁ -C₄ -alkyl, C₁ -C₄ -alkoxy, phenyl, which may bemethyl-, methoxy- or chlorine-substituted, benzyl, which may be methyl-,methoxy- or chlorine-substituted, C₁ -C₄ -alkylsulfonyl, chlorine,bromine or C₁ -C₉ -alkoxycarbonyl, which may be interrupted by 1 or 2oxygen atoms in ether function, and

Q³ is cyano, nitro, C₁ -C₉ -alkoxycarbonyl, which may be interrupted by1 or 2 oxygen atoms in ether function, or C₁ -C₄ -alkylsulfonyl, one ormore yellow dyes of the formula X and/or XI ##STR13## where E¹, E², E³,E⁴ and E⁵ are independently of each other hydrogen, C₁ -C₄ -alkyl, C₁-C₄ -alkoxy, halogen or phenoxy,

and/or one or more blue anthraquinone dyes of the formula XII ##STR14##where one of the two radicals G¹ and G² is hydroxyl and the other isphenylamino, which may be substituted by hydroxyl, C₁ -C₄ -alkyl or C₁-C₄ -alkoxy, dye preparations comprising these dye mixtures, and the usethereof for dyeing or printing textile materials.

Textile dyes used in the automotive sector, for example for seat covers,have to meet high application requirements, since they have to cope atone and the same time with strong light and high temperatures. The mostimportant parameter accordingly is good hot lightfastness. This appliesespecially to dye mixtures, in particular those for trichromatic dyeing.

It is a further object of the present invention to provide novel dyemixtures having advantageous properties for use in the automotivesector. The novel mixtures shall possess in particular good hotlight-fastness and high color strength.

We have found that this object is achieved by the second-mentioned dyemixtures defined above.

B, U³, E¹, E², E³, E⁴, E⁵ and Q² are each for example methyl, ethyl,propyl, isopropyl, butyl, isobutyl or sec-butyl.

Q³ is, and Q² may also be, for example methylsulfonyl, ethylsulfonyl,propylsulfonyl, isopropylsulfonyl, butylsulfonyl, isobutylsulfonyl orsec-butylsulfonyl.

Q² may also be for example phenyl, 2-, 3- or 4-methylphenyl,2,4-dimethylphenyl, 2-, 3- or 4-methoxyphenyl, 2,4-dimethoxyphenyl, 2-,3- or 4-chlorophenyl, 2,4-dichlorophenyl, 2-methyl-4-chlorophenyl,2-methyl-4-methoxyphenyl, benzyl, 2-, 3- or 4-methylbenzyl, 2-, 3 - or4-methoxybenzyl or 2-, 3- or 4-chlorobenzyl.

Q¹ is, and Q² and Q³ may each also be, for example methoxycarbonyl,ethoxycarbonyl, propoxycarbonyl, isopropoxycarbonyl, butoxycarbonyl,isobutoxycarbonyl, secbutoxycarbonyl, pentyloxycarbonyl,isopentyloxycarbonyl, neopentyloxycarbonyl, tert-pentyloxycarbonyl,hexyloxycarbonyl, 2-methylpentyloxycarbonyl, heptyloxycarbonyl,2-methylhexyloxycarbonyl, octyloxycarbonyl, isooctyloxycarbonyl,2-ethylhexyloxycarbonyl, nonyloxycarbonyl or isononyloxycarbonyl.

E¹, E², E³, E⁴, E⁵ and Q² may each also be for example methoxy, ethoxy,propoxy, isopropoxy, butoxy, isobutoxy or sec-butoxy.

E¹, E², E³, E⁴ and E⁵ may each also be for example fluorine, chlorine orbromine.

G¹ or G² is for example phenylamino, 4-hydroxyphenylamino,4-methylphenylamino or 4-methoxyphenylamino.

Reference should be made to previous remarks for the definitions of R¹,R² and L.

Preference is given to dye mixtures comprising an azo dye of the formulaIX where one of U¹ and U² is amino and the other is a radical of theformula ##STR15## where L, R¹ and R² are each as defined above.

Preference is further given to dye mixtures comprising an azo dye of theformula IX where Q¹ is cyano or formyl, Q² is C₁ -C₄ -alkyl or chlorine,and Q³ is cyano.

Preference is further given to dye mixtures comprising an azo dye of theformula IX where U³ is methyl.

Preference is further given to dye mixtures comprising an azo dye of theformula IX where R² is C₁ -C₅ -alkanoyl and L is C₄ -C₈ -alkylene whichis interrupted by 1 or 2 oxygen atoms in ether function.

Particular preference is given to dye mixtures comprising an azo dye ofthe formula IX where L is a radical of the formula (CH₂)₂ O(CH₂)₂,(CH₂)₂ O(CH₂)₃, (CH₂)₃ O(CH₂)₃, (CH₂)₃ O(CH₂)₄ or (CH₂)₂ O(CH₂)₂O(CH₂)₂.

Particular preference is further given to dye mixtures comprising an azodye of the formula IX where R² is acetyl.

Particular preference is further given to dye mixtures comprising an azodye of the formula IX where Q¹ and Q³ are each cyano and Q² is C₁ -C₄-alkyl, in particular methyl.

Attention is further drawn to dye mixtures comprising at least 6 azodyes of the formula IX.

Attention is drawn especially to dye mixtures comprising from 6 to 12,particularly from 6 to 8 or from 10 to 12, azo dyes of the formula IX,in particular to dye mixtures comprising 8 azo dyes of the formula IX.

When the dye mixtures of the invention contain a dye of the formula XI,preference is given to those mixtures which include a dye of the formulaXIa ##STR16## where E¹, E², E⁴ and E⁵ are each either hydrogen or methyl

The weight ratio between the dyes IX, X, XI and/or XII can vary withinwide limits and depends in particular on the hue to be matched. Examplesof weight ratios between the dyes of the mixtures according to theinvention are as follows:

Mixtures of the dyes IX and X: from 2.0:98.0 to 99.8:0.2.

Mixtures of the dyes IX and XI: from 1.3:98.7 to 99.8:0.2.

Mixtures of the dyes IX and XII: from 1.8:98.2 to 98.1:1.9.

Mixtures of the dyes IX, XII and X: from 97.8:2.0:0.2 to 0.9:51.7:47.4,from 80.6:1.6:17.8 to 1.8:97.4:0.8, from 80.5:19.4:0.1 to 1.9:8.1:90.0.

Mixtures of the dyes IX, XII and XI: from 97.8:2.0:0.2 to 0.7:41.7:57.6,from 74.0:1.4:24.6 to 1.8:97.1:1.1, from 97.9:1.9:0.2 to 1.3:5.6:93.1.

The dyes of the formulae IX, X, XI and XII are known per se.

Dyes of the formula IX are known for example from U.S. Pat. No.4,855,412, U.S. Pat. No. 4,855,413 or EP-A-201 896.

The dye of the formula X is known as C.I. Solvent Yellow 163 (58 840).

Dyes of the formula XI are described for example in JP-A-281 666/1991.The unsubstituted dye (E¹ to E⁵ =H) is known under the name DisperseYellow 42 (C.I. 10 338).

The dye of the formula XII (G¹ =phenylamino, G² =hydroxyl) is known asC.I. Disperse Blue 77 (60 766).

The dye mixtures of the invention may further comprise up to 30% byweight, preferably up to 20% by weight, each percentage being based onthe total weight of the dyes IX, X, XI and/or XII, of one or moreshading dyes.

Suitable yellow to orange shading dyes are for example the followingdyes which are known per se and are usually commercially available:##STR17##

Suitable red shading dyes are for example the following dyes which areknown per se and are usually commercially available: ##STR18##

Suitable blue to violet shading dyes are for example the following dyeswhich are known per se and are usually commercially available: ##STR19##

The second-mentioned dye mixtures of the invention may include UVabsorbers. Suitable UV absorbers are for example those of the formulaXIII or XIV: ##STR20## where M¹ is hydrogen or chlorine,

M² and M³ are identical or different and each is independently of theother hydrogen or C₁ -C₈ -alkyl, which may be substituted by phenyl,

M⁴ is hydrogen or hydroxyl, and

M⁵ and M⁶ are identical or different and each is independently of theother hydrogen, hydroxyl, or C₁ -C₆ -alkoxy, which may be substituted byhydroxyl, C₁ -C₄ -alkoxy, C₁ -C₄ -alkanoyloxy or benzoyloxy.

Of particular suitability are UV absorbers of the formula XIIIa, XIIIb,XIVa, XIVb or XIVc ##STR21##

The UV absorbers can be used individually or else mixed with oneanother, in which case mixtures of different species of the formula XIIIor XIV or else mixtures of compounds of the formulae XIII and XIV aresuitable.

In general, the amount of UV absorber used is from 0 to 6% by weight,preferably from 2 to 4% by weight, each percentage being based on theweight of the textile material to be dyed.

The second-mentioned dye mixtures of the invention are prepared in aconventional manner, for example by mixing the respective components inthe stated weight ratio. If desired, the novel mixtures may includefurther components, for example dispersants, such as ligninsulfonates orsulfonation products of the reaction product of formaldehyde witharomatics, or other assistants. It is also possible to mixready-prepared dye preparations of the respective dye components orready-prepared dye preparations with pure dyes.

Dye preparations based on the second-mentioned novel dye mixturescontain in general from 10 to 60% by weight, based on the weight of thedye preparation, of an above-defined dye mixture and also from 40 to 90%by weight, based on the weight of the dye preparation, of dispersants,further assistants and/or water.

The second-mentioned novel dye mixtures are useful for dyeing orprinting textile materials. For the purposes of the present inventiontextile materials are such as fibers, knitted fabrics or woven fabricsmade of polyester, modified polyester, e.g. anionically modifiedpolyester, or blends of polyesters with cellulose, cotton, viscose orwool. The dyeing and printing methods are known per se. Details can alsobe found in the Examples. Attention is drawn in particular to the use ofthese dye mixtures for dyeing or printing textile materials used in theautomotive sector.

The second-mentioned dye mixtures of the invention, which have highcolor strength, are notable for high hot lightfastness (FAKRA, DIN 75202), even under conditions of high energy of irradiation (testing inaccordance with SAE J1 885, 601 kJ). They produce dyeings of highreproducibility (pH and reduction stability). They have high colorstrength, high fastness values (eg. rub fastness, perspiration fastness,water droplet fastness, water fastness or solvent fastness) and a highcontact heat stability.

The following examples illustrate the invention. The percentage data inExamples 1 to 7 in respect of the composition of the dye mixtures arethe surface area percentages resulting from the respective HPLCinvestigations.

EXAMPLE 1

a) 16.3 g of 2-amino-3,5-dicyano-4-methylthiophene were dissolved withcooling in 250 g of 65% strength by weight sulfuric acid. 31.5 g ofnitrosylsulfuric acid (40% strength by weight) were added dropwise tothis solution with further cooling at from 0° to +5° C. and the mixturewas-stirred for 1.5 h at this temperature.

b) A mixture of 17 g of water-moist2-chloro-3-cyano-4-methyl-6-aminopyridine and the corresponding6-chloro-2-amino isomer (calculated dry and obtained by the processdescribed in DE-A-2,260,827), 20 ml of isobutanol, 11.8 g of1-amino-8-hydroxy-4-oxaoctane, 4.7 g of 1-amino-5-hydroxy-3-oxapentaneand 8 g of sodium carbonate was stirred at from 145° to 150° C. for 5 hunder a descending condenser. After cooling to 100° C., 35 ml of aceticacid and, at 35° to 40° C. with slight cooling, 15 g of 96% strength byweight sulfuric acid were added dropwise. After stirring for 3 hours,about 92% of the four hydroxy compounds was acetylated.

c) The solution of the diazonium salt described in a) was allowed to runinto the well-stirred mixture of the coupling components thus obtained,300 g of ice and 100 ml of water, and the mixture was stirred at from 0°to 5° C. for about 2 h. The product was filtered off with suction,washed until neutral and dried at 100° C. under reduced pressure.

The resulting brown powder consists of the 8 dye species:

    ______________________________________                                         ##STR22##                                                                    1.     W.sup.1 =                                                                             H                   5.2%                                              W.sup.2 =                                                                             (CH.sub.2).sub.3O(CH.sub.2).sub.4OH                            2.     W.sup.1 =                                                                             (CH.sub.2).sub.3O(CH.sub.2).sub.4OH                                                               2.5%                                              W.sup.2 =                                                                             H                                                              3.     W.sup.1 =                                                                             H                   39.6%                                             W.sup.2 =                                                                             (CH.sub.2).sub.3O(CH.sub.2).sub.4OCOCH.sub.3                   4.     W.sup.1 =                                                                             (CH.sub.2).sub.3O(CH.sub.2).sub.4OCOCH.sub.3                                                      18.8%                                             W.sup.2 =                                                                             H                                                              5.     W.sup.1 =                                                                             H                   6.2%                                              W.sup.2 =                                                                             (CH.sub.2).sub.2O(CH.sub.2).sub.2OH                            6.     W.sup.1 =                                                                             (CH.sub.2).sub.2O (CH.sub.2).sub.2OH                                                              2.4%                                              W.sup.2 =                                                                             H                                                              7.     W.sup.1 =                                                                             H                   15.1%                                             W.sup.2 =                                                                             (CH.sub.2).sub.2O(CH.sub.2).sub.2OCOCH.sub.3                   8.     W.sup.1 =                                                                             (CH.sub.2).sub.2O(CH.sub.2).sub.2OCOCH.sub.3                                                      6.7%                                              W.sup.2 =                                                                             H                                                              ______________________________________                                    

A dispersion of this dye mixture dyes polyester yarn package (PES) at130° C. without filter effect to a 2/1 standard depth in a brilliant redshade.

EXAMPLE 2

a) The reaction mixture obtained in Example 1 b) was mixed with 20 ml ofwater before treatment with acetic acid and brought to a pH of 5 withhydrochloric acid. The organic phase was separated off, dissolved inwater at a pH of 3 using further hydrochloric acid and coupled with thediazonium salt described in Example 1 a). By buffering with sodiumhydroxide solution to a pH of 4, filtering off with suction, washingwith hot water and drying at 100° C., a powdered dye mixture wasobtained. It contained the following components:

    ______________________________________                                         ##STR23##                                                                    1.          W.sup.1 =                                                                              H                                                                    W.sup.2 =                                                                              (CH.sub.2).sub.3O(CH.sub.2).sub.4OH                      2.          W.sup.1 =                                                                              (CH.sub.2).sub.3O(CH.sub.2).sub.4OH                                  W.sup.2 =                                                                              H                                                        3.          W.sup.1 =                                                                              H                                                                    W.sup.2 =                                                                              (CH.sub.2).sub.2O(CH.sub.2).sub.2OH                      4.          W.sup.1 =                                                                              (CH.sub.2).sub.2O(CH.sub.2).sub.2OH                                  W.sup.2 =                                                                              H                                                        ______________________________________                                    

b) For partial acetylation, 47.5 g of this dye mixture were stirredunder reflux for 4 h in 110 ml of glacial acetic acid. Crystallizationwas effected by adding 110 ml of water under reflux and subsequentlystirring for 1 hour. By squeezing off at room temperature and washingwith hot water, a crystalline press material was obtained, thedispersion of which when dyeing polyester yarn packages shows no crystalgrowth and accordingly a filter effect no longer occurs. The brownsuction filter material has a melting point of 188° to 190° C.

The individual species of Example 1 are present here in the followingratios:

    ______________________________________                                                    1.   4.4%                                                                     2.   2.0%                                                                     3.  41.7%                                                                     4.  17.6%                                                                     5.   5.6%                                                                     6.   2.1%                                                                     7.  16.2%                                                                     8.   6.1%                                                         ______________________________________                                    

EXAMPLE 3 (Comparison)

The use of 1-amino-5-hydroxy-3-oxapentane is dispensed with in Example1b and 17 g of 1-amino-8-hydroxy-4-oxaoctane are used instead. Aprocedure analogue to that of Example 2 is then followed and a dyemixture is obtained, as is described in similar form in Example 1 ofU.S. Pat. No. 4,855,413. The individual species are represented thereinin the following ratios:

    ______________________________________                                                    1.  32.4%                                                                     2.   7.8%                                                                     3.  45.2%                                                                     4.  11.6%                                                         ______________________________________                                    

When dyeing PES yarn packages from dispersion, the greenish dye powder(M.p.: 185° to 190° C.) shows a filter effect on the dyed material.

Changes in the acylation conditions with respect to time, temperature orthe water content of the acylation mixture only change the degree ofacetylation insubstantially and do not lead to acceptable yarn dyeings.

Perfect yarn dyeings are furthermore guaranteed if in Examples 1 and 2instead of 2-amino-5-hydroxyoxapentane the amines shown in the followingTable 1 are used in the mole fractions given.

The dye mixtures then in each case consist of six individual dyes:

                                      TABLE 1                                     __________________________________________________________________________    Example no.                                                                          Amine radical     Mol %                                                                             Crystal color                                                                        M.p.                                      __________________________________________________________________________            ##STR24##        20  brown  174-180                                   5      (CH.sub.2).sub.3O(CH.sub.2).sub.2OC.sub.2 H.sub.5                                               50  brown  190-196                                   6                                                                                     ##STR25##        50  brown  181-190                                   __________________________________________________________________________

EXAMPLE 7

If, in Example 1, 1-amino-8-hydroxy-4-oxaoctane is replaced by theequivalent amount of 1-amino-8-hydroxy-4,7-dioxaoctane and the furtherprocedure is as described in Example 2, a mixture of six dyes results ofthe composition:

    ______________________________________                                         ##STR26##                                                                    1.     W.sup.1 =                                                                             H                   43.7%                                             W.sup.2 =                                                                             (CH.sub.2).sub.3O(CH.sub.2).sub.2OCH.sub.3                     2.     W.sup.1 =                                                                             (CH.sub.2).sub.3O(CH.sub.2).sub.2OCH.sub.3                                                        22.1%                                             W.sup.2 =                                                                             H                                                              3.     W.sup.1 =                                                                             H                   5.8%                                              W.sup.2 =                                                                             (CH.sub.2).sub.2O(CH.sub.2).sub.2OH                            4.     W.sup.1 =                                                                             (CH.sub.2).sub.2O(CH.sub.2).sub.2OH                                                               2.8%                                              W.sup.2 =                                                                             H                                                              5.     W.sup.1 =                                                                             H                   16.2%                                             W.sup.2 =                                                                             (CH.sub.2).sub.2O(CH.sub.2).sub.2OCOCH.sub.3                   6.     W.sup.1 =                                                                             (CH.sub.2).sub.2 O(CH.sub.2).sub.2OCOCH.sub.3                                                     6.7%                                              W.sup.2 =                                                                             H                                                              ______________________________________                                    

(M.p.: 177° C.), the PES yarn dyeings of which turn out to be faultlessup to 2/1 standard depth of shade.

If, in Example 2, the diazonium salt is replaced by that of the aminesshown in the following Table 2, the dyes are obtained as mixtures having8 components, the composition of which in each case only differsinsubstantially from that of Example 2. They also have good dyeingproperties.

                                      TABLE 2                                     __________________________________________________________________________    Example No.                                                                          Amine                 Color shade on PES                               __________________________________________________________________________     8                                                                                    ##STR27##            red                                               9                                                                                    ##STR28##            red                                              10                                                                                    ##STR29##            violet                                           11                                                                                    ##STR30##            red                                              12                                                                                    ##STR31##            scarlet                                          13                                                                                    ##STR32##            red                                              14                                                                                    ##STR33##            red                                              15                                                                                    ##STR34##            blue-violet                                      16                                                                                    ##STR35##            medium blue                                      17                                                                                    ##STR36##            blue-violet                                      18                                                                                    ##STR37##            bluish red                                       19                                                                                    ##STR38##            red                                              20                                                                                    ##STR39##            violet                                           21                                                                                    ##STR40##            blue                                             22                                                                                    ##STR41##            orange                                           23                                                                                    ##STR42##            yellowish red                                    24                                                                                    ##STR43##            red                                              25                                                                                    ##STR44##            yellowish violet                                 26                                                                                    ##STR45##            yellow                                           27                                                                                    ##STR46##            yellow                                           28                                                                                    ##STR47##            yellow                                           29                                                                                    ##STR48##            red                                              30                                                                                    ##STR49##            bluish red                                       31                                                                                    ##STR50##            violet                                           __________________________________________________________________________

Dyeing Method

5 g of polyester fabric (PES) are introduced at 50° C. into 100 ml of adyeing liquor which contains a below-specified dye mixture and whose pHhas been adjusted to 4.5 with acetic acid/sodium acetate. After 5minutes at 50° C. the liquor is raised to 130° C., held at that levelfor 45 minutes and then cooled down to 70° C. over 20 minutes.

Thereafter the dyed polyester fabric is reduction cleared by treating itat 70° C. for 15 minutes in 200 ml of liquor containing per liter 5 mlof 32% strength by weight sodium hydroxide solution, 3 g of sodiumdithionite and 1 g of an addition product of 48 mol of ethylene oxidewith 1 mol of castor oil. The fabric is finally rinsed, neutralized withdilute acetic acid, rinsed once more and dried.

The following dye mixtures were used:

    __________________________________________________________________________    Dye mixture 32                                                                                           Amount based on PES                                Formula                    [% by weight]                                      __________________________________________________________________________     ##STR51##                 0.15                                               __________________________________________________________________________

b) Mixture of the following dyes:

    __________________________________________________________________________     ##STR52##                0.02                                                __________________________________________________________________________      W.sup.1 =    H                                                                W.sup.2 =    (CH.sub.2).sub.3O(CH.sub.2).sub.4OH                              W.sup.1 =    (CH.sub.2).sub.3O(CH.sub.2).sub.4OH                              W.sup.2 =    H                                                                W.sup.1 =    H                                                                W.sup.2 =    (CH.sub.2).sub.3O(CH.sub.2).sub.4OCOCH.sub.3                     W.sup.1 =    (CH.sub.2).sub.3O(CH.sub.2).sub.4OCOCH.sub.3                     W.sup.2 =    H                                                                W.sup.1 =    H                                                                W.sup.2 =    (CH.sub.2).sub.2O(CH.sub.2).sub.2OH                              W.sup.1 =    (CH.sub.2).sub.2O(CH.sub.2).sub.2OH                              W.sup.2 =    H                                                                W.sup.1 =    H                                                                W.sup.2 =    (CH.sub.2).sub.2O(CH.sub.2).sub.2OCOCH.sub.3                     W.sup.1 =    (CH.sub.2).sub.2O(CH.sub.2).sub.2OCOCH.sub.3                     W.sup.2 =    H                                                              __________________________________________________________________________    c)                                                                               ##STR53##              0.06                                                d)                                                                               ##STR54##              1.2                                                 __________________________________________________________________________    Dye mixture 33                                                                                          Amount based on PES                                 Formula                   [% by weight]                                       __________________________________________________________________________    a)                                                                               ##STR55##              0.06                                                b)                                                                              Mixture of the following dyes:                                                 ##STR56##              0.02                                                __________________________________________________________________________      W.sup.1 =    H                                                                W.sup.2 =    (CH.sub.2).sub.3O(CH.sub.2).sub.4OH                              W.sup.1 =    (CH.sub.2).sub.3O(CH.sub.2).sub.4OH                              W.sup.1 =    H                                                                W.sup.2 =    (CH.sub.2).sub.3O(CH.sub.2).sub.4OCOCH.sub.3                     W.sup.1 =    (CH.sub.2).sub.3O(CH.sub.2).sub.4OCOCH.sub.3                     W.sup.2 =    H                                                                W.sup.1 =    H                                                                W.sup.2 =    (CH.sub.2).sub.2O(CH.sub.2).sub.2OH                              W.sup.1 =    (CH.sub.2).sub.2O(CH.sub.2).sub.2OH                              W.sup.2 =    H                                                                W.sup.1 =    H                                                                W.sup.2 =    (CH.sub.2).sub.2O(CH.sub.2).sub.2OCOCH.sub.3                     W.sup.1 =    (CH.sub.2).sub.2O(CH.sub.2).sub.2OCOCH.sub.3                     W.sup.2 =    H                                                              __________________________________________________________________________    c)                                                                               ##STR57##              0.08                                                d)                                                                               ##STR58##              1.2                                                 __________________________________________________________________________

The following values were found:

Dye mixture 32 ΔE_(ab) ^(*) <1.5

Dye mixture 33 ΔE_(ab) ^(*) <1.0

(The ΔE_(ab) * value was determined under the L*a*b* color system (CIE1976).)

We claim:
 1. A dye mixture comprising at least one red azo dye of theformula IX ##STR59## where one of U¹ and U² is a radical of the formula##STR60## and the other is a radical of the formula NH-B, where L is C₂-C₈ -alkylene, which may be interrupted by 1 or 2 oxygen atoms in etherfunction,R¹ is hydrogen or C₁ -C₄ -alkyl, which may be substituted byhydroxyl, C₁ -C₄ -alkoxy or C₁ -C₈ -alkanoyloxy, R² is hydrogen, C₁ -C₄-alkyl, benzyl, phenyl or C₁ -C₈ -alkanoyl and B is hydrogen, C₁ -C₄-alkyl which may be hydroxyl-substituted, or a radical of the formulaL-O-R², where L and R² are each as defined above, U³ is hydrogen or C₁-C₄ -alkyl, Q¹ is cyano, formyl, nitro or C₁ -C₉ -alkoxycarbonyl, whichmay be interrupted by 1 or 2 oxygen atoms in ether function, Q² ishydrogen, C₁ -C₄ -alkyl, C₁ -C₄ -alkoxy, phenyl, which may be methyl-,methoxy- or chlorine-substituted, benzyl, which may be methyl-, methoxy-or chlorine-substituted, C₁ -C₄ -alkylsulfonyl, chlorine, bromine or C₁-C₄ -alkoxycarbonyl, which may be interrupted by 1 or 2 oxygen atoms inether function, and Q³ is cyano, nitro, C₁ -C₉ -alkoxycarbonyl, whichmay be interrupted by 1 or 2 oxygen atoms in ether function, or C₁ -C₄-alkylsulfonyl, mixed with at least one dye selected from the groupconsisting of dyes of the formulae X, XI and XII where dyes of theformulae X and XI are yellow dyes ##STR61## where E¹, E², E³, E⁴ and E⁵are independently of each other hydrogen, C₁ -C₄ -alkyl, C₁ -C₄ -alkoxy,halogen or phenoxy, and dyes of the formula XII are blue anthraguinonedyes ##STR62## where one of the two radicals G¹ and G² is hydroxyl andthe other is phenylamino, which may be substituted by hydroxy, C₁ -C₄-alkyl or C₁ -C₄ -alkoxy, the dye of formula IX and each dye of formulaX, XI or XII present in the dye mixture being present in amount adequateto match a selected hue different from that matched by any individualdye.
 2. A dye mixture as claimed in claim 1, wherein one of U¹ and U² isNH₂ and the other is a radical of the formula ##STR63## where L, R¹ andR² are each as defined in claim
 1. 3. A dye mixture as claimed in claim1, comprising at least 6 azo dyes of the formula IX.
 4. A dye mixture asclaimed in claim 1, further comprising up to 30% by weight based on thetotal weight of said dye mixture of one or more shading dyes.
 5. Amethod of dying or printing a textile material which comprises applyingto said textile material a dye mixture as claimed in claim
 1. 6. The dyemixture of claim 1 containing dyes of formulae IX and X, wherein the dyeof formula IX is present in amount of at least 2 parts and the dye offormula X in an amount of at least 0.2 parts based on 100 parts of thecombined weight of dyes of formulae IX and X.
 7. The dye mixture ofclaim 1 containing dyes of formulae IX and XI, wherein the dye offormula IX is present in amount of at least 1.3 parts and the dye offormula XI in an amount of at least 0.2 parts based on 100 parts of thecombined weight of dyes of formulae IX and XI.
 8. The dye mixture ofclaim 1 containing dyes of formulae IX and XII, wherein the dye offormula IX is present in amount of at least 1.8 parts and the dye offormula XII in an amount of at least 1.9 parts based on 100 parts of thecombined weight of dyes of formulae IX and XII.
 9. The dye mixture ofclaim 1 containing dyes of formulae IX, X and XII, wherein the dye offormula IX is present in amount of at least 0.9 parts, the dye offormula X in an amount of at least 0.1 parts and the dye of formula XIIin an amount of at least 1.6 parts based on 100 parts of the combinedweight of dyes of formulae IX, X and XII.
 10. The dye mixture of claim 1containing dyes of formulae IX, XI and XII, wherein the dye of formulaIX is present in amount of at least 0.7 parts, the dye of formula XI inan amount of at least 0.2 parts and the dye of formula XII in an amountof at least 1.4 parts of the combined weight of dyes of formulae X, XIand XII.
 11. A dye preparation comprising 10-60% by weight of the dyemixture of claim 1 and 40 to 90% of at least one of a dye assistant andwater.